Novel thia-alkanols

ABSTRACT

NOVEL TIA-ALKANOLS OF THE FORMULA   R-CH(-OH)-CH(-R1)-S-A   USEFUL AS PESTICIDES, LUBRICANT ADDITIVES AND INTERMEDIATES FOR SURFACANTS AND TO A NOVEL PROCESS FOR THEIR PREPARATION.   R-CH(-OH)-CH(-R1)-S-   WHEREIN RI IS AN ALIPHATIC GROUP OF 1 TO 22 CARBON ATOMS, R1 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALIPHATIC GROUP OF 1 TO 21 CARBONS WITH THE SUM OF CARBON ATOMS IN R AND R1 BEING 4 TO 22 AND R AND R1, TAKEN TOGETHER WITH THE ETHYLENE GROUP TO WHICH THEY ARE ATTACHED FORM A CYCLOALIPHATIC RING OF 6 TO 12 CARBON ATOMS AND A IS SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND CYCOALIPHATIC OF 6 TO 24 CARBON ATOMS OPTIONALLY SUBSTITUTED WTH ONE OR MORE GROUPS OF THE FORMULA

United States Patent 3,729,518 NOVEL THIA-ALKANOLS Herbert LepperCologne-Mulheim, Wilfried Umbach,

Langenfeld, Rhineland, and Werner Stein, Erkrath- Unterbach, Germany,assignors to Henkel & Cie., GmbH, Dusseldorf-Holthausen, Germany NoDrawing. Filed Sept. 10, 1970, Ser. No. 71,214 Claims priority,application Germany, Sept. 25, 1969, P 19 48 385.3 Int. Cl. C07c 149/14US. Cl. 260-609 A 1 Claim ABSTRACT OF THE DISCLOSURE Novel thia-alkanolsof the formula RCHCIJHSA wherein R is an aliphatic group of 1 to 22carbon atoms, R is selected from the group consisting of hydrogen andaliphatic group of 1 to 21 carbon atoms with the sum of carbon atoms inR and R being 4 to 22 and R and R taken together with the ethylene groupto which they are attached form a cycloaliphatic ring of 6 to 12 carbonatoms and A is selected from the group consisting of aliphatic andcycloaliphatic of 6 to 24 carbon atoms optionally substituted with oneor more groups of the formula RoH-oH-s useful as pesticides, lubricantadditives and intermediates for surfactants and to a novel process fortheir preparation.

OBJECTS OF THE INVENTION It is an object of the invention to provide thenovel thia-alkanols of Formula I.

It is another object of the invention to provide a novel process for thepreparation of the thia-alkanols of Formula I without a catalyst and atnormal temperatures.

These and other objects and advantages of the invention will becomeobvious from the following detailed description.

THE INVENTION The novel thia-alkanols of the invention have the formulaRCHCH-SA wherein R is an aliphatic group of 1 to 22 carbon atoms, R isselected from the group consisting of hydrogen and aliphatic group of 1to 21 carbon atoms with the sum of carbon atoms in R and R being 4 to 22and R and R taken together with the ethylene group to which they areattached form a cycloaliphatic ring of 6 to 22 carbon atoms and A isselected from the group consisting of aliphatic and cycloaliphatic of 6to 24 carbon atoms optionally substituted with one or more groups of theformula R-CH(|)HS- E R1 The substituent A may contain one or more doublebonds and may be substituted with groups such as ethers, esters,halogens, nitro, etc. and may be interrupted by hetero atoms. When A isaliphatic, it may be straight chain or branched chain. When A iscycloaliphatic, it may have several rings and may have straight orbranched chain alkyl substituents. Preferably A is aliphatic of 6 to 18carbon atoms or cycloaliphatic of 6' to 12 carbon atoms Patented Apr.24, 1973 ice in the ring and may be substituted with 1, 2 or 3 groups ofthe formula RCH-CH-S- R and R or the cycloaliphatic ring formed by R andR and the ethylene to which they are attached may be optionallysubstituted and/ or interrupted by hetero atoms and/or hetero atomgroups such as others, esters, halogens, nitro, etc. and thecycloaliphatic ring may be substituted with straight or branched-chainalkyl. When R and R are aliphatic, they may be branched or straightchain. Preferably, R is a saturated aliphatic of 1 to 16 carbon atomsand R is hydrogen or saturated aliphatic of 1 to 15 carbon atoms withthe total number of carbon atoms in R and R is 4 to 16 or R and Rtogether 'with the ethylene to which they are attached form a saturatedaliphatic of 6 to 12 carbon atoms.

The compounds of Formula I may be made by known methods such as reactingalkali metal mercaptides with a compound of the formula wherein X is ahalogen or by reacting an alkyl halide with an alkali metal mercaptideof the formula MeSCHzCH-R H wherein Me is an alkali metal or by reactinga mercaptan with an unsymmetrical epoxide in the presence of a basiccatalyst.

However, the preferred method and the novel method of the invention forthe preparation of the compounds of Formula I comprises reacting at atemperature of 0 to 100 C. a hydroxyalkyl mercaptan of the formulaR-CH-CH-R (IJH SH (II) wherein R and R have the above definition with amono or polyunsaturated olefinic compound having 6 to 24 carbon atoms toform the corresponding compound of Formula I. The reaction is preferablyeffected at 20 to C. at normal pressure.

In the method of the invention, no catalyst is needed for the reactionand no separation step is needed to remove catalyst from the product andthere are no undesired by-products produced such as alkali metal halidesas in the case of the process using alkali metal mercaptides.

Very reactive olefins such as ethylene are known to react withZ-mercapto ethanol and Z-hydroxy-l-mercaptopropane to form thecorresponding fl-hydroxyalkyl alkyl sulfides but this reaction requiresrelatively high reaction temperatures and pressures and long reactiontimes such as 16 hours at 150 C. and atmospheres pressure. The processof the invention unexpectedly reacts long chainZ-hydroxy-l-mercapto-alkanes and liquid olefins without pressure at roomtemperature Without the addition of a catalyst. This high degree ofreactivity of the long chain Z-htydroxy-l-mercapto-alkanes is even moresurprising since unsubstituted l-mercapto alkanes of the same chainlength will not react or only slightly react with the same olefins underthe identical reaction conditions. This occurs in spite of the fact thatthe thiyl radical R-CH CI-I -S formed as an intermediate during thelatter radical addition must be more easily formed than the thiylradical RCI-IOHCH -S- of the present process which is made less stabledue to the negative inductive effect of the ,B-hydroxy group.

The Z-hydroxy-l-mercapto-alkanes of Formula II can be advantageouslyprepared by reacting epoxides with hydrogen sulfide in the presence of acatalytic amount of base as described in copending, commonly assignedUS. application Ser. No. 818,441, now US. Pat. No. 3,637,- 864 and Ser.No. 818,444, now abandoned, both filed Apr. 22, 1969 and Ser. No.863,387 filed Oct. 2, 1969. Ex-

initiators such as peroxides, are necessary so that a separation offoreign materials is also not required The products of the process areutilisable in many ways In pest control they can be used as insecticidesand fungicides, they serve as valuable additives in the lubriamples ofsuitable Z-hydroxy-l-mercapto-alkanes are 2- cant field, as for example,as oxidation and corroslon hydroxy-l-mercapto-hexane,2-hydroxy-l-mercapto-cycloretarders, extreme-pressure additives, sludgedispersing hexane, Z-hydroxy-l-mercapto-octane,2-hydroxy-1-mersubstances, foam regulators, or antioxidants for rubbercapto-dodecane, 2-hydroxy-l-rnercapto-octodecane and compositions, andmay further also be used as emulsifiers. 2-mercapto-3-hydroxy-octane.They are also valuable starting materials for other The monoorpoly-unsaturated olefinic compounds reactions such as alkoxylations,sulfonations and so on, with 6 to 24 carbon atoms used as startingmaterials may which lead to products having a surface-active nature andbe straight or branched-chain compounds with terminal may be used aswetting agents or as textile assistants in and/or non-terminal doublebonds, and may also be sub- Washing and cleaning compositions. Furtherclasses of stituted or interrupted by hetero-atoms or hetero-atomcompound which are available starting from 2-hydroxygroups which do notupset the reaction such as, etherdialkylsulfides areB-hydroxy-substituted sulfoxides, suloxygen, alkoxyor ester-groups.Preferably monoor fones, sulfonium and sulfoxonium compounds.poly-unsaturated aliphatic compounds with 6 to 18 car- In the followingexamples there are described several bon atoms and/or monoorpolyunsaturated cyclO- preferred embodiments to illustrate theinvention. Howaliphatic compounds with 6 to 12 carbon atoms in the ever,it should be understood that the invention is not ring are used in theprocess of the invention. Examples intended to be limited to thespecific embodiments. of such compounds are: hexene, hexadiene-1,5,n-octene- Example 1 1, n-octene-2, n-dodecene-l, n-octadecene-l, methylester A f 56 0 5 1 f t 1 d 81 of undecylenic acid, n-decatriene-l,4,9,n-octatrieneg g f a 0 an 1,3,6, n-octatriene-1,3,7, cyclohexene,cyclooctene, cyclo- 1 1 0 y'd f p 5 dodecene, cyclohexadiene,cyclooct-adiene and bicyclored ours at an t fireactlon mlx was thendistilled to obtain a 71% yield of Z-hydroxyoctyl 1 lfid '11 b '1 t r140 146 c t 0 05 The olefinic compounds may be reacted singly or in Octy6 Wu a 9 3 0 f 3 admixture with one another. In the case of aliphatic Hg3 riffractlve m 2 57 d 6 compounds, olefinic mixtures of chain lengthscorrespond- Product 2 ur i 0 (ca Cu 2: ing to those obtained by crackingor dehydrohalogena- 7 an 5 6 Structure 1 was con me tion, by the Zieglerprocess, by oligoand co-oligo-merisaby its mfrare spectrum i Its f m' fh tion of conjugated dienes or dienes with mono-olefines, In Order toIllustrate t e Surpnsmg y gh O t e may also be used process of thelnvention, the same reaction was effected The reaction between theolefinic compound and the at dlflerent temperFtures t g g l f; iB-hydroxyalkylmercaptan may be effected with a molar Wlth the Yle tame e,g ratio of 1:1 to 1:12, n being the number of the double reactlon of 56(0-05 mo) 0 ifi 3, bonds present in the olefinic compound. Normally itis mol) of bmercaptomwct? g not necessary to use an excess ofhydroxymercaptan or sulfide- The results are Shown Ta 6 olefin. However,the reaction is preferably carried out 40 TABLE I with the molar ratioof olefin to fi-hydroxyalkylmercaptan Temp, m of m; of 1:1 to 1:3. Thereaction of mono-olefins with fl-hy- Sterling n o 0. reaction ylelddroxyalkylmercaptans is preferably effected in the molarZ-hydroxy-l-mercapto-n-octane 30 g ratio 1:1 40

The use of a solvent in the reaction is generally un- 60 1 9 necessary,but it may be of advantage in certain cases, 20 4 0 such as whenreaction mixtures of high viscosity are lmmcaptonomm 30 2 0 formed. Ifnecessary, organic solvents such as dioxane, :8 f g isopropanol,tetrahydrofuran, digylcol dimethyl ether may 60 1 3 be used The workingup of the reaction mixtures may be Examples 2 to 9 carried out bydistillation or by recrystallisation and the Using the procedure fExample 1 5 l f h unreacted starting materials may be used again withouta 2 1 lk and 05 l f the 1 5 further Purification Operation, 50 that theSYPtheSeS may set forth in Table II were reacted and after distillingoff be Carried out both discontinuously contlfluously unreacted startingmaterials the final products of Table The proc ss of the inven i n imark d y P ul r II were crystallized from ethanol. The structure of thesimplicity of operation No special measures such as exfinal products wasconfirmed by their infrared and NMR clusion of air or moisture, oraddition of catalysts or spectra.

TABLE II Refrac- Reaction B1. (1), tive Temp, timein M.P. (2), index,Percent Example Reaction components 0. hours Product C.) nu yield 2-n-Hexene-l and 2-hydroxy-1- 25 2 2-hydroxyhexyl-hexylsulfide (1)79-81/0.03 1.4707 81 mercapto-hexane. mm. Hg. 3 n-Decene-l and2-hydroxy-l- 40 2 2-hydroxyhexyl-decyl-sul.fide (1) 188l90/0.16 1.4711

mercapto-hexane. mm. Hg. 4 n-Octenc-Z and 2-hydroxy-1- 50 32-hydr0xy0cty1-1-methy1-heptyl- (1) 111120/0.01 1. 4760 40mercapto-octane. sulfide. mm. Hg. 5 n-Dodecene-l and Z-hydroxy-l- 50 22-hydroxyoctyl-dodecyl-sulfide (2) 2243---. 63

mercapto-l-octane. 6 n-Dodecene-l and 2-hydroxy-1- 70 2Z-hydroxyocta-deeyl-dodecyl-sulfide. (2) 5960 72 mercapto-oetadecane. 7n-Octadecene-l and 2-hydr0xy-L 25 2 Zhydroxyoctyl-octadecyl-sulfide (2)51-52 64 mercapto-octane. 8 n-Octadecene-l and 2-hydroxy-1- 65 32-hydroxyocta-decyl-octadecyl- (2) 76-76 mercapto-octadecane. sulfide. 9Methyl ester of n-undecenc-ldcan 60 3 Methylesterof12-thia-(14)-hydroxy-(2) 68-69 66 boxylic acid and 2-hydroxy-1-n1ercapto-octadecar1e.

triacontanoic acid.

Example 10* Example 11 Using the procedure of Example 10, 9.2 g. (0.1mol) of bicyclo-(2,2,1)-heptadiene-(2,5) were reacted with 16.2 g. (0.1mol) of an isomeric mixture of 2-hydroxy-3- mercapto-octane and3-hydroxy-2-mereapto-octane to obtain a 93% yield of an isomeric mixtureboiling at 118- 126 C. at 0.03 mm. Hg and having a refractive index of n9=1.5095.

Example 12 68 g. (0.5 mol) of n-decatriene-1,4,9 were stirred for hoursat 40 C. with 218 g. (1 mol) of 2-hydroxy-1- mercapto-dodecane and afterdistilling off the unreacted starting material, there was obtained an88% yield of 13,24-di-thia-1 1,26-dihydroxy-hexatriacontene-( 17 meltingat 63-64" C. after recrystallization from acetone.

Example 13 21.8 g. (0.2 mol) of cyclooctadiene-1,5 and 43.6 g. (0.2 mol)of 2-hydr0xy-l-mercapto-dodecane were stirred for 4 hours at a reactiontemperature of 25 C. By working up the reaction mixture by distillation,there was obtained an 81% yield of [fl-hydroxy-dodecylrnercapto]-cyclooctene-(4) with a boiling point of 130142 C. at 0.03 mm. and arefractive index n =1.4790.

Example 14 9.2 g. (0.1 mol) of bicyclo-[2,2,l]-heptadiene-2,5 and 13.2g. (0.1 mol) of 2-hydroxy-1-mercapto-cyclohexane were reacted at 25 C.for one hour to obtainafter distillation of the reaction mixture an 80%yield of an isomeric mixture of 3-[B-hydroxycyclohexylmercapto]-tricyclo-[2,2,1,0 ]-heptane and 2-[3-hydroxycyclohexylmercapto]-bicyclo-[2,2,1]-heptene-(5) boiling at 114-126 C. at 0.05 mm. and having a refractive index of n =1.5452.

Various modifications of the products and process of the invention maybe made without departing from the spirit and scope thereof and it is tobe understood that the invention is to be limited only as defined in theappended claim.

We claim:

1. A thia-alkanol of the formula wherein R is an aliphatic hydrocarbongroup of 1 to 22 carbon atoms, R is selected from the group consistingof hydrogen and aliphatic hydrocarbon group of 1 to 21 carbon atoms withthe sum of carbon atoms in R and R being 4 to 22 and R and R takentogether with the ethylene group to which they are attached, form acycloaliphatic hydrocarbon ring of 6 to 12 carbon atoms and A isselected from the group consisting of aliphatic hydrocarbon of 6 to 18carbon atoms and cycloaliphatic hydrocarbon having 6 to 12 carbon atomssubstituted with one to two groups of the formula R-OH-CH-S- ReferencesCited UNITED STATES PATENTS 2,776,997 1/1957 Doumaji 260609 A 2,927,9463/1960 Petty 260-609 D 3,328,467 6/ 1967 Hamilton 260-609 AX 3,522,3147/1970 Warner 260-609 A 2,768,975 10/1956 Scharmann 260609 B FOREIGNPATENTS 209,078 6/ 1940 Switzerland 260-609 F 208,875 5/19'40Switzerland 260-609 F 208,874 5/1940 Switzerland 260-609 F 208,8735/1940 Switzerland 260 609 F 202,243 4/ 1939 Switzerland 260-609 FLEjWIS GOTTS, Primary Examiner D. R. PHILLIPS, Assistant Examiner US.Cl. X.R.

25245; 260609 B, 609 A, 609' E, 607 A, 607 B; 424-327

